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Refining/Petrochemical Integration –A New ParadigmAnil Khatri, GTC TechnologyCoking and CatCracking ConferenceNew Delhi - October 2013
• Present integration schemes focus on propylene, and miss the potential to capture added value from aromatics
• Valuable components exist in FCC gasoline – heavy olefins & aromatics
• Patented GTC purification and conversion technology can upgrade traditional fuel components to high value petrochemicals
Presentation Themes
Component Value Relative to Unleaded Gasoline
Naphtha 0.87
Unleaded Gasoline 1.00
Toluene 1.13
Benzene 1.15
Ethylene 1.24
Mixed Xylenes 1.26
Paraxylene 1.43
Propylene 1.55
Styrene 1.63
Benzene Toluene Mixed Xylenes
CH3CH3
CH3
Propylene
Page 2
Presentation Overview
Gasoline demand and clean fuel regulations around the world
Process for recovering aromatics from FCC Gasoline -GT-BTX-PluS®
Processes for utilization of FCC olefins
Case study – No gasoline, only p-xylene and benzene
Page 3
World Gasoline Demand – Stagnant or Decreasing
Unit: 1,000 B/D 2006 2008 2010 2012*
US
Gasoline Demand 10,929 11,120 11,340 10,850
Gasoline Surplus (Deficit) (1,135) (1,100) (870) (200)
EUROPE
Gasoline Demand 2,546 2,430 2,334 2,250
Gasoline Surplus (Deficit) 902 1,000 1,200 1,150
MIDEAST GULF
Gasoline Demand 1,193 1,368 1,545 1,750
Gasoline Surplus (Deficit) (250) (120) (200) (300)
ASIA PACIFIC
Gasoline Demand 3,966 4,210 4,505 4,800
Gasoline Surplus (Deficit) 150 250 300 200
Major Regions Gasoline Supply/Demand
Source: Asian Pacific Energy Consulting * Estimated
Page 4
Gasoline Specification
1993/1995 2000 2005 CURRENT
Vehicle Emission Standard Equivalent Euro II Euro III Euro IV Euro V U.S.
Sulfur, ppm, max 1,000/500 150 50 (10) 10 30
Aromatics, vol%, max - 42 35 35 25
Olefins, vol%, max - 18 18 18 8.5
Benzene, vol%, max 5.0 1.0 1.0 1.0 0.62
Limitation Imposed on Aromatics
Page 5
Conventional Three-Stage Process
ULSGasolineBlendingMCN
70-150oCFCC
Naphtha
LCN
C5-iC6-
HCN
150oC-EP
FCC Gasoline Desulfurization
(optional)
Saturation(unavoidable)
Desulfurization(needed)
Severe HDS
Medium HDS
Mild HDS
CausticExtraction
C6-C9 Olefins Sulfur
Page 7
Aromatics Extraction with GT-BTX PluS®
Solvent
Raffinate: Paraffins + Olefins
Extract: Sulfur + Aromatics
Aromatics
H2 H2S
ULSGasolineBlending
MCN
70-150oC
FCCNaphtha
LCN
C5-iC6-
HCN
150oC-EP
(optional)
ULSGasolineBlending
GT-BTX PluS®
Severe HDS
HDS
Mild HDS
CausticExtraction
Page 8
RaffinateExtract
Feed
H2O
Solvent
Liquid-liquid Extraction
Extract
Solvent
Raffinate
Feed
Extractive Distillation
Aromatics Extraction Alternatives
Page 9
Different Solvent Systems for Aromatics Recovery
Solvent S/FRelative volatility (α)
n-C7/benzene
Techtiv (GT-BTX®) 3.0 2.44Sulfolane 3.0 2.00N-methyl pyrrolidone 3.0 1.95N-formyl morpholine 3.0 1.89Tri-ethylene glycol 3.0 1.44Tetra-ethylene glycol 3.0 1.39Glycol blends (CAROM) 3.0 1.35No solvent 0 0.57
(α) R.V. = (yA/xA)/(yB/xB)Page 10
GT-BTX PluS® - General Flow Scheme
HydrocarbonFeed
Aromatics-rich solvent
Lean solvent Raffinate
Extractive Distillation Column (EDC)
Solvent Recovery Column (SRC)
Aromatics to downstream fractionation
Page 11
Typical Refinery Configuration with GT-BTX PluS® - Products to Gasoline
• Zero Δ in octane value• Low benzene• Low sulfur
FCCUGT-BTX PluS
Kerosene
Gasoil
Wide Naphtha Range
Fuel
FCCNaphtha
Crude Oil
Desulfurization
Gasoline
Cru
de D
istil
latio
n
Olefinic Raffinate to Gasoline
Gasoline
Isomerization
Naphtha Reforming
Hydrotreating
Gasoline
Page 12
Typical Refinery Integrated with Aromatics using GT-BTX PluS®
Much preferred to recycling FCC naphtha to catalytic reforming
NaphthaReforming
FCCU
Hydrotreating Isomerization
Aromatics Plant
GT-BTX PluS
Kerosene
Gasoil
Wide Naphtha Range
Fuel
FCCNaphtha
BenzeneToluene
Heavy AromaticsCrude OilXylenes
Desulfurization
Fuel
Cru
de D
istil
latio
n
Page 13
Options for FCC C4+ Olefins
• Gasoline blending zero change in octane value desulfurizedde-benzenized
• Aromatization BTX, PX
• Re-cracking C3=
Page 14
Steam Cracker heavy olefins
FCC C6 –C8, non-aromatic cut
Dry Gas
Aromatics
LPG
FCC C4/C5
Aromatization: Generate BTX from Low Value Streams
Page 15
More Aromatics from Non-Traditional Feedstock
Additional Aromatics from FCC C4 – C8 Olefin Fraction
NaphthaReforming
FCCU
Hydrotreating Isomerization
Aromatics Plant
GT-BTX PluS
Kerosene
Gasoil
Wide Naphtha Range
Fuel
FCCNaphtha
Benzene Toluene
Heavy AromaticsCrude OilXylenes
Desulfurization
Fuel
Cru
de D
istil
latio
n
Aromatization C6-C8C4-C5
Page 16
Refinery configuration with GT-BTX PluS®
to facilitate increased Propylene
NaphthaReforming
FCCU
Hydrotreating Isomerization
Additional Propylene
GT-BTX PluS
Kerosene
Gasoil
Wide Naphtha Range
Fuel
FCCNaphtha
Crude Oil
Desulfurization
Fuel
Cru
de D
istil
latio
n
Fuel
Aromatics
Olefinic Raffinate
Extends Range of FCC Naphtha RecyclePage 17
GT-BTX PluS® - Enabling Technology
• Technically advanced extraction process enables
Desulfurized gasoline to < 15 ppm sulfur with zero octane loss
Reduced benzene in cracked gasoline to < 0.5% benzene
FCC olefins preserved for conversion to aromatics or propylene
Patented process – available through GTC Technology
Page 18
Case Study – GT-BTX PluS®& GT-Aromatization℠
Part of a recent project implemented for Rafinerie Onesti
*Stream is sent to Aromatics Complex for Benzene and Paraxylene recovery
Liquid Product
C6-C8 Cut
C9-C10
Olefinic Raffinate H2 Off Gas
C6-C10 Aromatics*
LPG + Off Gas
H2 Off Gas
Pygas C11+
C4-C5 Cut
Heavies
HDS
Prim
ary
Frac
tiona
tion
Pygas Selective HDT
GT-BTX PluS
AromatizationUnit
High-severity FCC feed
Pygas
Page 19
Incremental Aromatics from Gasoline Source
C6-C9 AROMATICS KG/HR TPA
INDIGENOUS FCC 11,427 97,126
PYGAS 8,029 68,245
AROMATIZATION 26,525 225,471
TOTAL 45,981 390,842
Total incremental BTX = 320 KTA
Page 20
Conclusions
Refinery/Petrochemical integration involves more than simple propylene recovery
Recycling FCC gasoline to naphtha reforming is not true integration, and misses the main point of process efficiency
GT-BTX PluS® is the enabling technology which permits the best use of molecules to their highest value
Page 21